WO2020209208A1 - Antifouling coating composition - Google Patents

Antifouling coating composition Download PDF

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Publication number
WO2020209208A1
WO2020209208A1 PCT/JP2020/015399 JP2020015399W WO2020209208A1 WO 2020209208 A1 WO2020209208 A1 WO 2020209208A1 JP 2020015399 W JP2020015399 W JP 2020015399W WO 2020209208 A1 WO2020209208 A1 WO 2020209208A1
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Prior art keywords
acrylate
meth
copolymer
monomer
group
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PCT/JP2020/015399
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French (fr)
Japanese (ja)
Inventor
慧 小林
崇 松木
英典 和久
拓也 安井
基道 伊藤
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日東化成株式会社
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Publication of WO2020209208A1 publication Critical patent/WO2020209208A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • the present invention relates to an antifouling coating composition.
  • Aquatic pollutants such as Fujitsubo, Serupura, Murasakiigai, Fusakokemushi, Hoya, Green laver, Sea lettuce, Slime, etc. Adhesion causes problems such as impairing the functions of those ships and impairing their appearance.
  • an antifouling paint composition is applied to a ship or the like to form an antifouling coating film, and an antifouling agent is gradually released from the antifouling coating film to prevent fouling over a long period of time.
  • Patent Document 1 A technique for exerting performance is known (Patent Document 1).
  • Patent Document 1 Even if the technology of Patent Document 1 is adopted, the coating film portion that is constantly submerged in seawater maintains long-term antifouling performance, but in the draft portion, which is the boundary between water and water, sunshine or the like There was a problem that the antifouling property was not fully exhibited because it was affected by various factors such as being easily affected by.
  • the present invention has been made in view of such circumstances, and the coating film dissolution continues for a long period of time even after being exposed to sunlight for a long period of time, and it is also good in a draft part where aquatic polluted organisms are likely to adhere. It is an object of the present invention to provide a composition for forming an antifouling coating film having high environmental safety, which can exhibit excellent antifouling performance.
  • an antifouling coating composition containing a resin component R and fired kaolin, wherein the resin component R is a copolymer A or an organopolysiloxane B having a cross-linking reactive functional group.
  • the copolymer A is a copolymer of the monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a), and the monomer ( In a), an antifouling coating composition represented by the general formula (1) is provided.
  • (meth) acrylic means acrylic or methacrylic.
  • the antifouling paint composition of the present invention contains a resin component R and calcined kaolin.
  • Resin component R The resin component R is a copolymer A or an organopolysiloxane B having a cross-linking reactive functional group.
  • Copolymer A is a copolymer of the monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a).
  • Copolymer A contains monomeric units derived from the monomers (a) and (b).
  • the monomer (a) is a triorganosilyl monomer (meth) acrylate and is represented by the general formula (1).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 to R 4 represent the same or different branched alkyl group or phenyl group having 3 to 8 carbon atoms, respectively).
  • the branched alkyl group of R 2 ⁇ R 4 having 3 to 8 carbon atoms for example, isopropyl, isobutyl, s- butyl, t- butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methyl Pentyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, texyl group, cyclohexyl group, 1,1-dimethylpentyl group, 1-methylhexyl group, 1,1-dimethylhexyl group, 1-methyl Examples thereof include heptyl group, 2-methylbutyl group, 2-ethylbutyl group, 2,2-dimethylpropyl group, cyclohexylmethyl group, 2-ethylhexyl group, 2-propylpentyl group and 3-methylpentyl group.
  • R2 to R4 are an isopropyl group, an s-butyl group, a t-butyl group, a phenyl group, and a 2-ethylhexyl group. Particularly preferred are an isopropyl group and a 2-ethylhexyl group.
  • Examples of the monomer (a) include triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, and triisopentylsilyl (meth) acrylate.
  • Preferred examples thereof include triisopropylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, and tri2-ethylhexylsilyl (meth) acrylate.
  • These monomers (a) can be used alone or in combination of two or more.
  • the monomer (b) is an ethylenically unsaturated monomer other than the monomer (a), and is, for example, a (meth) acrylic acid ester, a vinyl compound, an aromatic compound, a dialkyl ester compound of a dibasic acid, or the like. Can be mentioned.
  • Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and (meth).
  • vinyl compound examples include vinyl compounds having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone. Be done.
  • aromatic compound examples include styrene, vinyltoluene, ⁇ -methylstyrene and the like.
  • dialkyl ester compound of dibasic acid examples include dimethyl maleate, dibutyl maleate, dimethyl fumarate and the like.
  • these monomers (b) can be used alone or in combination of two or more.
  • (meth) acrylic acid ester is preferable from the viewpoint of coating material properties, and methyl methacrylate, butyl (meth) acrylic acid, and (meth) acrylic acid are particularly preferable from the viewpoint of crack resistance.
  • the monomer (a) in the copolymer A is preferably 5 to 75% by mass, more preferably 30 to 60% by mass.
  • the content of the monomer (a) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75% by mass. , It may be within the range between any two of the numerical values exemplified here.
  • the coating film solubility is particularly good.
  • the weight average molecular weight (Mw) of the copolymer A is 5000 to 300,000. This is because if the molecular weight is less than 5,000, the coating film of the antifouling paint becomes fragile and easily peels or cracks, and if it exceeds 300,000, the viscosity of the polymer solution increases, making handling difficult.
  • this Mw is, for example, 5000, 10000, 20000, 30000, 40,000, 50000, 60000, 70000, 80000, 90000, 100000, 200,000, 300,000, and is between any two of the numerical values exemplified here. It may be within the range.
  • Examples of the method for measuring Mw include gel permeation chromatography (GPC method).
  • the copolymer A is a copolymer of a random copolymer of a monomer (a) and a monomer (b), an alternating copolymer, a periodic copolymer, or a block copolymer. You may.
  • the copolymer A can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.
  • polymerization initiator examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2,4-dimethylvaleronitrile).
  • the polymerization initiators can be used alone or in combination of two or more.
  • the polymerization initiators include, in particular, 2,2'-azobisisobutyronitrile and 2,2'-azobis (2). -Methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate is preferable.
  • the molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.
  • polymerization method examples include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, non-aqueous dispersion polymerization and the like.
  • solution polymerization or non-aqueous dispersion polymerization is particularly preferable in that copolymer A can be obtained easily and accurately.
  • an organic solvent may be used if necessary.
  • the organic solvent is not particularly limited, but for example, an aromatic hydrocarbon solvent such as xylene and toluene; an aliphatic hydrocarbon solvent; an ester solvent such as ethyl acetate, butyl acetate, isobutyl acetate and methoxypropyl acetate; isopropyl.
  • Alcohol-based solvents such as alcohol, butyl alcohol and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be mentioned.
  • butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene and xylene are preferable.
  • These solvents can be used alone or in combination of two or more.
  • the reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually 50 to 160 ° C, preferably 60 to 150 ° C.
  • the polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
  • Organopolysiloxane B is an organopolysiloxane having a cross-linking reactive functional group.
  • the crosslinkable functional group is preferably provided on a silicon atom in the molecular chain.
  • cross-linking reactive functional group examples include an alkoxy group such as a hydroxyl group, a methoxy group, an ethoxy group and a propoxy group; and an aralkyloxy group such as a benzyloxy group.
  • organic group examples include organic groups generally possessed by organopolysiloxane, and specifically, alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl group. , Alkenyl group such as allyl group; aralkyl group such as benzyl group; aryl group such as phenyl group and naphthyl group; alkyl halide group such as 3,3,3-trifluoropropyl group and the like.
  • Organopolysiloxane B forms an organopolysiloxane rubber by a condensation reaction in the presence of a catalyst and in the presence of moisture (which may be moisture in the air).
  • the cross-linking reactive functional group in the organopolysiloxane B forms a silicone rubber by condensation reaction with the cross-linking reactive functional group of another organopolysiloxane B or the hydrolyzable group in the cross-linking agent. , Becomes a film.
  • the reaction temperature in such a condensation reaction is usually 80 ° C. or lower, preferably 50 ° C. or lower.
  • the weight average molecular weight of the organopolysiloxane B is preferably 400 to 1,000,000, more preferably 2000 to 150,000, and even more preferably 4000 to 80,000. Two or more kinds having different weight average molecular weights can be used in combination. Specifically, the weight average molecular weight is, for example, 400, 2000, 4000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 100000, 150,000, 500000, 1000000, and the numerical values exemplified here are used. It may be within the range between any two.
  • organopolysiloxane B Commercially available products of organopolysiloxane B include RF-5000, RF-10000 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), XIAMETER OHG-4010 Polymer, XIAMETER OHG-4012 Polymer (above, manufactured by Dow Corning), XC96- 723, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, YR3204 (above, Momentive Performance Materials), BLUESIL FLD 48V3500 (above, Elchem), POLYMER FD 6 (Wacker Chemie), DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-9931, FMS-9922 (Gelest) Made) and the
  • Calcined Kaolin Calcined kaolin was dehydroxylated from naturally occurring hydrous kaolin (kaolinite, a hydrous aluminosilicate with a theoretical composition [Al 2 Si 2 O 5 (OH) 4 ]) that is naturally produced by thermal methods. Kaolin transformed into a form. Firing changes the kaolin structure from crystalline to amorphous, among other properties. The calcination is carried out by heat-treating the coarse or fine hydrous kaolin, for example at a temperature in the range of 500 ° C. to 1200 ° C., for example, at a temperature in the range of 800 ° C. to 1200 ° C., by any known method. To.
  • Examples of the commercially available calcined kaolin include Translink 445 (manufactured by BASF), Satintone W, Satintone 5, and Satintone 5HB (manufactured by BASF Corporation).
  • the whiteness of the calcined kaolin is preferably 75% or more, and more preferably 80% or more. Whiteness is measured by the measuring method defined by ISO2469.
  • the average particle size of the calcined kaolin is preferably 0.1 to 5.0 ⁇ m, more preferably 0.4 to 2.0 ⁇ m.
  • the average particle size is determined by, for example, a known method of sedimentation of particulate matter in a fully dispersed state in an aqueous medium using a Sedigraf® 5100 particle size analyzer manufactured by Micromeritics (Atlanta, Ga). Measured at.
  • the average particle size is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1. 0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 3.0, 4.0, It is 5.0 and may be in the range between any two of the numerical values exemplified here.
  • the content of calcined kaolin in the composition of the present invention is not particularly limited, but is usually 1 to 40% by mass, preferably 5 to 20% by mass in terms of solid content.
  • the content of calcined kaolin is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 , 20, 25, 30, 35, 40% by mass, and may be within the range between any two of the numerical values exemplified here.
  • Antifouling agents examples include inorganic agents and organic agents.
  • the inorganic drug examples include cuprous oxide, copper thiocyanate (generic name: copper rodan), copper powder and the like.
  • copper cuprous oxide and copper rodane are particularly preferable, and copper cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, ricitin, mineral oil, etc., has long-term stability during storage. Is more preferable.
  • organic agents examples include 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-zinc oxide (generic name: zinc pyrithione), and zinc ethylenebisdithiocarbamate (generic name: dineb).
  • the content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 60% by mass, preferably 1 to 50% by mass in terms of solid content.
  • the content of the antifouling agent is, for example, 0.1, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass, and here. It may be in the range between any two of the illustrated values.
  • additives may be added to the antifouling paint resin of the present invention, if necessary.
  • the other additives include a resin component other than the copolymer A, an elution adjuster, a plasticizer, a pigment, a dye, a defoaming agent, a dehydrating agent, and shaking. Examples include agents and organic solvents.
  • the resin component R is organopolysiloxane B
  • other additives include plasticizers, pigments, dyes, defoamers, fillers, dehydrators, shakers, crosslinkers, condensation catalysts, and bleed oils. , Organic solvent and the like.
  • the polymer P is a polymer obtained by polymerizing the monomer (b).
  • the monomer (b) is any ethylenically unsaturated monomer other than the monomer (a).
  • the monomer (b) used for the polymerization of the polymer P may have the same composition as or different from the monomer (b) used for the polymerization of the copolymer A.
  • the monomer (b) can be used alone or in combination of two or more, and in particular, from the viewpoint of compatibility with the copolymer A, methyl (meth) acrylate and ethyl (meth) acrylate.
  • the content of the polymer P in the composition of the present invention is not particularly limited, but the content ratio with the copolymer A is usually 0 in terms of solid content and the mass ratio (polymer P / copolymer A). It is .1 to 9.0, preferably 0.1 to 4.0.
  • Examples of the elution adjuster include monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof.
  • Examples thereof include the salt thereof or the alicyclic hydrocarbon resin. These can be used alone or in combination of two or more.
  • Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
  • Examples of the commercially available alicyclic hydrocarbon resin include Quinton 1500, 1525L, 1700 (trade name, manufactured by Zeon Corporation).
  • rosin, rosin derivative, naphthenic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, or metal salts thereof are preferable, and rosin and rosin derivative are more preferable.
  • plasticizer examples include phosphoric acid esthetics, phthalates, adipates, sebacic acid esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, and vaseline.
  • plasticizer examples include polybutene, tristrimellitic acid (2-ethylhexyl), silicone oil, and chlorinated paraffin. These can be used alone or in combination of two or more.
  • dehydrating agent examples include calcium sulfate, synthetic zeolite-based adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbodiimidazoles. These can be used alone or in combination of two or more.
  • Examples of the filler include an inorganic filler and / or an organic filler.
  • Examples of the inorganic filler include calcium carbonate, precipitated barium sulfate, barite powder, titanium oxide, silica soil, aluminum hydroxide, fine granular alumina, magnesium oxide, magnesium carbonate, talc, zeolite, bentonite, silica powder, and phthalocyanine blue. , Carbon black and the like.
  • Examples of the organic filler include synthetic resin powders such as polypropylene, polyvinyl chloride, polystyrene, and acrylic silicone.
  • Examples of the rocking agent include fatty acid amide, polyethylene oxide, silica, fumed silica and the like. These can be used alone or in combination of two or more.
  • cross-linking agent examples include acetoxy having an acetoxy group such as diacetoxymethylsilane, diacetoxydimethylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane, triacetoxyvinylsilane, tetraacetoxysilane, ethyltriacetoxysilane, and diacetoxymethylphenylsilane.
  • acetoxy having an acetoxy group such as diacetoxymethylsilane, diacetoxydimethylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane, triacetoxyvinylsilane, tetraacetoxysilane, ethyltriacetoxysilane, and diacetoxymethylphenylsilane.
  • Silanes having ketooxime groups such as silane, methyltri (butanoxime) silane, vinyltri (butanoxime) silane, phenyltri (butanoxime) silane, propyltri (butanoxime) silane, methyltriisopropenoxysilane, triisopropenoxysilane, tetraprope
  • Examples thereof include silanes having an alkenoxy group such as noxysilane, phenyltrialkenoxysilane, isopropylpropenoxysilane, butyltripropenoxysilane, and vinyltripropenoxysilane, and one of these may be used alone or in combination of two or more. Can be used in combination.
  • condensation catalyst examples include an organic tin compound such as dibutyltin diacetate and an organic titanium compound such as tetraisopropyl titanate, and one of these can be used alone or in combination of two or more.
  • bleed oil examples include silicone oil, a graft copolymer composed of an acrylic polymer and dimethylpolysiloxane, perfluoropolyether oil, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and poly.
  • oxyethylene castor oil and polyoxyethylene cured castor oil examples of these compounds can be used alone or in combination of two or more.
  • the bleed oil has excellent compatibility with the organopolysiloxane rubber formed by the condensation reaction of the organopolysiloxane B. Therefore, according to the composition of the present invention, it is possible to suitably form a coating film having excellent coating film performance in which peeling and the like are unlikely to occur.
  • organic solvent examples include xylene, toluene, hexane, heptane, octane, cyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, butyl acetate, methanol, ethanol, propanol, isopropyl alcohol, isoamyl alcohol, n-butanol, 1 -Methoxy-2-propanol, glycol-based ester, aromatic hydrocarbon, aliphatic hydrocarbon, white spirit, alicyclic hydrocarbon-based solvent, naphthenic hydrocarbon, mineral spirit, aliphatic solvent naphtha, low boiling point aromatic Examples include naphtha, isoparaffin, normal paraffin and the like. These organic solvents can be used alone or in combination of two or more.
  • the antifouling coating composition of the present invention is produced by mixing and dispersing, for example, a mixed solution containing resin component R, calcined kaolin, other additives, etc. using a disperser. It can. It is also possible to produce by adding calcined kaolin after mixing and dispersing a mixed solution containing the resin component R, an antifouling agent, other additives and the like using a disperser.
  • the mixed solution is preferably one in which various materials such as resin component R and calcined kaolin are dissolved or dispersed in a solvent.
  • the solvent the same solvent as the above organic solvent can be used.
  • the disperser for example, one that can be used as a fine pulverizer can be preferably used.
  • a commercially available homomixer, sand mill, bead mill, disper, paint shaker or the like can be used.
  • the mixed solution may be mixed and dispersed by using a container provided with a stirrer to which glass beads or the like for mixing and dispersing are added.
  • the antifouling coating composition of the present invention may be composed of one liquid or a plurality of liquids (for example, two liquids).
  • the resin component R is an organopolysiloxane B
  • a plurality of liquids are formed, and at least one of the condensation catalyst and the cross-linking agent is mixed in a liquid different from the organopolysiloxane B and then mixed immediately before use as a paint. Is preferable. This improves storage stability.
  • an antifouling coating film is formed on the surface of the coating film to be formed using the above antifouling coating composition.
  • the antifouling coating film is gradually dissolved from the surface and the surface of the coating film is constantly updated, so that adhesion of aquatic polluted organisms can be prevented.
  • the coating film-forming product include ships (particularly the bottom of ships), fishing gear, underwater structures, and the like.
  • the thickness of the antifouling coating film may be appropriately set according to the type of the coating film to be formed, the navigation speed of the ship, the seawater temperature, and the like. For example, when the coating film to be formed is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 700 ⁇ m, preferably 100 to 600 ⁇ m.
  • % In each production example, example and comparative example indicates mass%.
  • the weight average molecular weight (Mw) is a value (polystyrene conversion value) obtained by GPC.
  • the conditions of GPC are as follows.
  • Naphthezol 160 Naphthenic solvent manufactured by JXTG Energy Co., Ltd.
  • Examples and Comparative Examples Manufacturing of Paint Composition
  • a coating composition was produced by blending the components shown in Tables 2 to 5 in the proportions (mass%) shown in the table and mixing and dispersing them with glass beads having a diameter of 1.5 to 2.5 mm.
  • the antifouling coating composition of Examples and Comparative Examples shown in Table 5 had a two-component structure consisting of a liquid a having a component a and a liquid b having a component b.
  • Copper oxide Product name "NC-301” (manufactured by Nissin Chemco Co., Ltd.) Copper thiocyanate (I): Product name “Copper thiocyanate (I)” (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Copper Pirition: Product name "Copper Omagin” (manufactured by LONZA Co., Ltd.) Zinc pyrithione: Product name “Zinc pyrithione” (manufactured by LONZA Co., Ltd.) Zineb: Product name “Zineb” (manufactured by SIGMA-ALDRICH) SeaNine211: 4,5-dichloro-2-n-octyl-3-isothiazolone (manufactured by R & H, 30% xylene solution of active ingredient) Medetomidine: Product name "Selektope” (manufactured by Aitec) Econea 028
  • DMS-S35 Trade name "DMS-S35", manufactured by Gelest, polydimethylsiloxane having both terminal silanol groups, Mw 49000 DMS-S32: Trade name “DMS-S32", manufactured by Gelest, polydimethylsiloxane having both terminal silanol groups, Mw 36000 YR3204: Trade name "YR3204", manufactured by Momentive, polymethylphenylsiloxane (90% solution) having both terminal silanol groups.
  • Polyether-modified silicone oil Trade name "KF-6020" Side-chain polyethylene oxide and polypropylene oxide-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Polyether / long-chain alkyl / aralkyl-modified silicone oil Trade name "X-22-2516" Side-chain polyethylene oxide, polypropylene oxide, long-chain alkyl, aralkyl-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Polyoxyethylene (30) lanolin Product name "NIKKOL TW-30" (manufactured by Nikko Chemicals Co., Ltd.)
  • Methylphenyl silicone oil Product name "KF-50” (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Dibutyltin dilaurate Di-n-butyltin dilaurate, trade name "Neostan U-100" (manufactured by Nitto Kasei)
  • TES40 WN Partially hydrolyzed condensate of tetraethoxysilane
  • Example 1 to 23 and Comparative Examples 1 to 6 the coating composition was applied to both sides of a hard vinyl chloride plate (100 ⁇ 200 ⁇ 2 mm) as a dry coating film so as to have a thickness of about 200 ⁇ m.
  • the obtained coating film was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 200 ⁇ m.
  • Examples 24 to 26 and Comparative Example 7 an epoxy-based primer HEMPADUR QUATTRO XO 17870 (manufactured by HEMPEL) was applied on a hard vinyl chloride plate (110 ⁇ 60 ⁇ 2 mm) with a dry film thickness of about 100 ⁇ m, and then further silicon-based. Tiecoat HEMPASIL NEXUS X-TEND 27500 (manufactured by HEMPEL) was applied in a dry film thickness of about 100 ⁇ m. A mixture of solutions a and b of the antifouling coating composition obtained in Examples and Comparative Examples was applied thereto with a dry film thickness of about 200 ⁇ m, and dried at room temperature for 3 days to prepare a test plate. ..
  • This test plate was exposed to solar radiation outdoors at an angle of 45 ° from the ground facing south, and the state of the coating film after 3 months and 6 months was evaluated. The evaluation was performed by the following method. ⁇ : There is no abnormality at all. X: Cracks are seen in the coating film. ⁇ Immersion test after weather resistance test> After performing the above weather resistance test for 6 months, the test plate was immersed 1.5 m below the sea level in Owase City, Mie Prefecture to stain the test plate with deposits after 6 months, 12 months, and 18 months. Observed after 24 months. The evaluation was performed by visually observing the state of the coating film surface, and judged according to the following criteria.
  • ⁇ There is no adhesion of polluted organisms such as shellfish and algae, and there is almost no slime.
  • ⁇ A level at which there is no attachment of polluted organisms such as shellfish and algae, and slime is thinly attached (to the extent that the coating film surface can be seen), but it can be lightly wiped off with a brush.
  • ⁇ There is no adhesion of polluted organisms such as shellfish and algae, but the slime is so thick that the coating film surface cannot be seen, and it cannot be removed even if it is wiped strongly with a brush.
  • ⁇ Level at which polluted organisms such as shellfish and algae are attached.

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Abstract

Provided is a composition for forming a highly environmentally safe antifouling coating film, said film being capable of maintaining coating film dissolution over a prolonged period of time even after long-term exposure to sunlight and exhibiting good antifouling performance even in a draft zone to which aquatic fouling organisms frequently attach.　The present invention provides an antifouling coating composition comprising a resin component R and calcined kaolin, wherein: the resin component R is a copolymer A or an organopolysiloxane B having a crosslinkable functional group; the copolymer A is a copolymer of a monomer (a) with an ethylenically unsaturated monomer (b) other than the monomer (a); and the monomer (a) is represented by general formula (1).

Description

防汚塗料組成物Antifouling paint composition
　本発明は、防汚塗料組成物に関する。 The present invention relates to an antifouling coating composition.
　フジツボ、セルプラ、ムラサキイガイ、フサコケムシ、ホヤ、アオノリ、アオサ、スライム等の水棲汚損生物が、船舶（特に船底部分）や漁網類、漁網付属具等の漁業具や発電所導水管等の水中構造物に付着することにより、それら船舶等の機能が害される、外観が損なわれる等の問題がある。 Aquatic pollutants such as Fujitsubo, Serupura, Murasakiigai, Fusakokemushi, Hoya, Green laver, Sea lettuce, Slime, etc. Adhesion causes problems such as impairing the functions of those ships and impairing their appearance.
　このような問題を防ぐために、船舶等に防汚塗料組成物を塗布して防汚塗膜を形成し、防汚塗膜から防汚薬剤を徐放させることによって、長期間に渡って防汚性能を発揮させる技術が知られている（特許文献１）。 In order to prevent such problems, an antifouling paint composition is applied to a ship or the like to form an antifouling coating film, and an antifouling agent is gradually released from the antifouling coating film to prevent fouling over a long period of time. A technique for exerting performance is known (Patent Document 1).
特開２０００－１７２０３号公報Japanese Unexamined Patent Publication No. 2000-17203
　しかし、特許文献１の技術を採用しても、海水中に常に没水されている塗膜部分は長期防汚性能を維持するものの、水中と水上との境界である喫水部においては、日照などの影響を受けやすいなど様々影響を受けることから、防汚性が十分に発揮されないという問題があった。 However, even if the technology of Patent Document 1 is adopted, the coating film portion that is constantly submerged in seawater maintains long-term antifouling performance, but in the draft portion, which is the boundary between water and water, sunshine or the like There was a problem that the antifouling property was not fully exhibited because it was affected by various factors such as being easily affected by.
　本発明はこのような事情に鑑みてなされたものであり、長期間太陽光に暴露された後においても長期間にわたり塗膜溶解が持続し、水棲汚損生物の付着が起こりやすい喫水部においても良好な防汚性能を発揮できる、環境安全性の高い防汚塗膜を形成するための組成物を提供するものである。 The present invention has been made in view of such circumstances, and the coating film dissolution continues for a long period of time even after being exposed to sunlight for a long period of time, and it is also good in a draft part where aquatic polluted organisms are likely to adhere. It is an object of the present invention to provide a composition for forming an antifouling coating film having high environmental safety, which can exhibit excellent antifouling performance.
　本発明によれば、樹脂成分Ｒおよび焼成カオリンを含有する防汚塗料組成物であって、前記樹脂成分Ｒは、共重合体Ａであるか、又は架橋反応性官能基を有するオルガノポリシロキサンＢであり、前記共重合体Ａは、単量体（ａ）と、前記単量体（ａ）以外のエチレン性不飽和単量体（ｂ）との共重合体であり、前記単量体（ａ）は、一般式（１）で表される、防汚塗料組成物が提供される。 According to the present invention, an antifouling coating composition containing a resin component R and fired kaolin, wherein the resin component R is a copolymer A or an organopolysiloxane B having a cross-linking reactive functional group. The copolymer A is a copolymer of the monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a), and the monomer ( In a), an antifouling coating composition represented by the general formula (1) is provided.
　本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、樹脂成分Ｒおよび焼成カオリンを含む組成物が、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventor has found that a composition containing a resin component R and calcined kaolin can solve the above problems, and has completed the present invention.
　以下、本発明について詳細を説明する。本明細書において、「（メタ）アクリル」は、アクリル、又はメタクリルを意味する。 Hereinafter, the present invention will be described in detail. As used herein, "(meth) acrylic" means acrylic or methacrylic.
１．防汚塗料組成物
　本発明の防汚塗料組成物は、樹脂成分Ｒおよび焼成カオリンを含有する。 1. 1. Antifouling paint composition The antifouling paint composition of the present invention contains a resin component R and calcined kaolin.
１－１．樹脂成分Ｒ
　樹脂成分Ｒは、共重合体Ａであるか、又は架橋反応性官能基を有するオルガノポリシロキサンＢである。 1-1. Resin component R
The resin component R is a copolymer A or an organopolysiloxane B having a cross-linking reactive functional group.
１－１－１．共重合体Ａ
　共重合体Ａは、単量体（ａ）と、単量体（ａ）以外のエチレン性不飽和単量体（ｂ）との共重合体である。共重合体Ａは、単量体（ａ）および（ｂ）に由来する単量体単位を含む。 1-1-1. Copolymer A
The copolymer A is a copolymer of the monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a). Copolymer A contains monomeric units derived from the monomers (a) and (b).
＜単量体（ａ）＞
　単量体（ａ）は、（メタ）アクリル酸トリオルガノシリル単量体であり、一般式（１）で表される。
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ１は水素原子又はメチル基、Ｒ２～Ｒ４はそれぞれ同一又は異なって炭素数３～８の分岐アルキル基又はフェニル基を示す） <Polymer (a)>
The monomer (a) is a triorganosilyl monomer (meth) acrylate and is represented by the general formula (1).
Figure JPOXMLDOC01-appb-C000002
 (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 to R 4 represent the same or different branched alkyl group or phenyl group having 3 to 8 carbon atoms, respectively).
　Ｒ２～Ｒ４の炭素数３～８の分岐アルキル基としては、例えば、イソプロピル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、１－エチルプロピル基、１－メチルブチル基、１－メチルペンチル基、１，１－ジメチルプロピル基、１，１－ジメチルブチル基、テキシル基、シクロヘキシル基、１，１－ジメチルペンチル基、１－メチルヘキシル基、１，１－ジメチルヘキシル基、１－メチルヘプチル基、２－メチルブチル基、２－エチルブチル基、２，２－ジメチルプロピル基、シクロヘキシルメチル基、２－エチルヘキシル基、２－プロピルペンチル基、３－メチルペンチル基等が挙げられる。Ｒ２～Ｒ４として好ましいものは、イソプロピル基、ｓ－ブチル基、ｔ－ブチル基、フェニル基、及び２－エチルヘキシル基である。特に好ましいものは、イソプロピル基、及び２－エチルヘキシル基である。 The branched alkyl group of R 2 ~ R 4 having 3 to 8 carbon atoms, for example, isopropyl, isobutyl, s- butyl, t- butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methyl Pentyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, texyl group, cyclohexyl group, 1,1-dimethylpentyl group, 1-methylhexyl group, 1,1-dimethylhexyl group, 1-methyl Examples thereof include heptyl group, 2-methylbutyl group, 2-ethylbutyl group, 2,2-dimethylpropyl group, cyclohexylmethyl group, 2-ethylhexyl group, 2-propylpentyl group and 3-methylpentyl group. Preferred as R2 to R4 are an isopropyl group, an s-butyl group, a t-butyl group, a phenyl group, and a 2-ethylhexyl group. Particularly preferred are an isopropyl group and a 2-ethylhexyl group.
　単量体（ａ）としては、例えば、（メタ）アクリル酸トリイソプロピルシリル、（メタ）アクリル酸トリイソブチルシリル、（メタ）アクリル酸トリｓ－ブチルシリル、（メタ）アクリル酸トリイソペンチルシリル、（メタ）アクリル酸トリフェニルシリル、（メタ）アクリル酸ジイソプロピルフェニルシリル、（メタ）アクリル酸ジイソプロピルイソブチルシリル、（メタ）アクリル酸ジイソプロピルｓ－ブチルシリル、（メタ）アクリル酸ジイソプロピルイソペンチルシリル、（メタ）アクリル酸イソプロピルジイソブチルシリル、（メタ）アクリル酸イソプロピルジｓ－ブチルシリル、（メタ）アクリル酸ｔ－ブチルジイソプチルシリル、（メタ）アクリル酸ｔ－ブチルジイソペンチルシリル、（メタ）アクリル酸ｔ－ブチルジフェニルシリル、（メタ）アクリル酸ジイソプロピルテキシルシリル、（メタ）アクリル酸ジイソプロピルシクロヘキシルシリル、（メタ）アクリル酸トリシクロヘキシルシリル、（メタ）アクリル酸トリ１，１－ジメチルペンチルシリル、（メタ）アクリル酸トリ２，２－ジメチルプロピルシリル、（メタ）アクリル酸トリシクロヘキシルメチルシリル、（メタ）アクリル酸ジイソプロピルシクロヘキシルメチルシリル、（メタ）アクリル酸トリ２－エチルヘキシルシリル、（メタ）アクリル酸トリ２－プロピルペンチルシリル等が挙げられる。好ましくは、（メタ）アクリル酸トリイソプロピルシリル、（メタ）アクリル酸トリｓ－ブチルシリル、（メタ）アクリル酸ｔ－ブチルジフェニルシリル、（メタ）アクリル酸トリ２－エチルヘキシルシリル等が挙げられる。これらの単量体（ａ）は、単独で又は２種以上を組み合わせて使用できる。 Examples of the monomer (a) include triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, and triisopentylsilyl (meth) acrylate. Triphenylsilyl acrylate, diisopropylphenylsilyl (meth) acrylate, diisopropylisobutylsilyl (meth) acrylate, diisopropyls-butylsilyl (meth) acrylate, diisopropylisopentylsilyl (meth) acrylate, (meth) acrylic Isopropyldiisobutylsilylate isopropyl, isopropyldis-butylsilyl (meth) acrylate, t-butyldiisoptylsilyl (meth) acrylate, t-butyldiisopentylsilyl (meth) acrylate, t-butyl (meth) acrylate Diphenylsilyl, diisopropyltexylsilyl (meth) acrylate, diisopropylcyclohexylsilyl (meth) acrylate, tricyclohexylsilyl (meth) acrylate, tri-1,1-dimethylpentylsilyl (meth) acrylate, (meth) acrylic acid Tri-2,2-dimethylpropylsilyl, tricyclohexylmethylsilyl (meth) acrylate, diisopropylcyclohexylmethylsilyl (meth) acrylate, tri2-ethylhexylsilyl (meth) acrylate, tri2-propylpentyl (meth) acrylate Cyril and the like can be mentioned. Preferred examples thereof include triisopropylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, and tri2-ethylhexylsilyl (meth) acrylate. These monomers (a) can be used alone or in combination of two or more.
＜単量体（ｂ）＞
　単量体（ｂ）は、単量体（ａ）以外のエチレン性不飽和単量体であり、例えば、（メタ）アクリル酸エステル、ビニル化合物、芳香族化合物、二塩基酸のジアルキルエステル化合物等が挙げられる。 <Polymer (b)>
The monomer (b) is an ethylenically unsaturated monomer other than the monomer (a), and is, for example, a (meth) acrylic acid ester, a vinyl compound, an aromatic compound, a dialkyl ester compound of a dibasic acid, or the like. Can be mentioned.
　（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸２一エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－メトキシプロピル、（メタ）アクリル酸４－メトキシブチル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸フェニル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸プロピレングリコールモノメチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸フルフリル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル、
メタクリル酸２－［２－（２－ヒドロキシエトキシ）エトキシ］エトキシ］エチル、こはく酸モノ（２－（メタ）アクリロイルオキシエチル）、Ｎ－（３－ジメチルアミノプロピル）（メタ）アクリルアミド、（メタ）アクリル酸２－［２－（２－メトキシエトキシ）エトキシ］エチル、Ｎ，Ｎ'－ジメチル（メタ）アクリルアミド、（メタ）アクリル酸２－（２－メトキシエトキシ）エチル、（メタ）アクリル酸、アクリル酸ヒドロキシプロピル、メタクリル酸２－（アセトアセチルオキシ）エチル、メタクリル酸２－（２－ヒドロキシエトキシ）エチル、Ｎ－ビニル－２－ピロリドン、アクリル酸２－［２－（２－エトキシエトキシ）エトキシ］エチル、
４－ヒドロキシブチルアクリレートグリシジルエーテル、Ｎ－イソポロピルアクリルアミド、アクリル酸２－（ジメチルアミノ）エチル、アクリル酸２－（２－エトキシエトキシ）エチル、アクリル酸４－ヒドロキシブチル、アクリル酸テトラヒドロフルフリル、アクリル酸３－クロロ－２－ヒドロキシプロピル、メタクリル酸２－［２－（２－エトキシエトキシ）エトキシ］エチル、Ｎ，Ｎ'－ジエチルアクリルアミド、アクリル酸３－メトキシブチル、等のアクリル酸エステル類、
等が挙げられる。 Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and (meth). ) Acrylic acid 21 ethylhexyl, (meth) acrylate lauryl, (meth) acrylate 2-methoxyethyl, (meth) acrylate 2-methoxypropyl, (meth) acrylate 4-methoxybutyl, (meth) acrylate benzyl , (Meta) phenyl acrylate, (meth) 2-ethoxyethyl acrylate, (meth) propylene glycol monomethyl acrylate, (meth) 2-hydroxyethyl acrylate, (meth) 2-hydroxypropyl acrylate, (meth) Glycidyl acrylate, flufuryl (meth) acrylate, tetrahydrofurfuryl acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
2- [2- (2-Hydroxyethoxy) ethoxy] ethoxy] ethyl methacrylate, mono (2- (meth) acryloyloxyethyl), N- (3-dimethylaminopropyl) (meth) acrylamide, (meth) 2- [2- (2-methoxyethoxy) ethoxy] ethyl acrylate, N, N'-dimethyl (meth) acrylamide, 2- (2-methoxyethoxy) ethyl (meth) acrylate, (meth) acrylic acid, acrylic Hydropyl acrylate, 2- (acetoacetyloxy) ethyl methacrylate, 2- (2-hydroxyethoxy) ethyl methacrylate, N-vinyl-2-pyrrolidone, 2- [2- (2-ethoxyethoxy) ethoxy] acrylate ethyl,
4-Hydroxybutyl acrylate glycidyl ether, N-isopolopylacrylamide, 2- (dimethylamino) ethyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 4-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, Acrylic acid esters such as 3-chloro-2-hydroxypropyl acrylate, 2- [2- (2-ethoxyethoxy) ethoxy] ethyl methacrylate, N, N'-diethylacrylamide, 3-methoxybutyl acrylate, etc.
And so on.
　ビニル化合物としては、例えば、塩化ビニル、塩化ビニリデン、アクリロニトリル、メタクリロニトリル、酢酸ビニル、安息香酸ビニル、ビニルブチレート、ブチルビニルエーテル、ラウリルビニルエーテル、Ｎ－ビニルピロリドン等の官能基を有するビニル化合物が挙げられる。 Examples of the vinyl compound include vinyl compounds having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone. Be done.
　芳香族化合物としては、例えば、スチレン、ビニルトルエン、α－メチルスチレン等が挙げられる。 Examples of the aromatic compound include styrene, vinyltoluene, α-methylstyrene and the like.
　二塩基酸のジアルキルエステル化合物としては、マレイン酸ジメチル、マレイン酸ジブチル、フマル酸ジメチル等が挙げられる。 Examples of the dialkyl ester compound of dibasic acid include dimethyl maleate, dibutyl maleate, dimethyl fumarate and the like.
　本発明においては、これら単量体（ｂ）を単独又は二種以上で用いることができる。特に、単量体（ｂ）としては、塗膜物性の観点から、（メタ）アクリル酸エステルが好ましく、特に耐クラック性の観点から、メタクリル酸メチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸２一エチルヘキシル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸フルフリル、（メタ）アクリル酸テトラヒドロフルフリル等がより好ましい。 In the present invention, these monomers (b) can be used alone or in combination of two or more. In particular, as the monomer (b), (meth) acrylic acid ester is preferable from the viewpoint of coating material properties, and methyl methacrylate, butyl (meth) acrylic acid, and (meth) acrylic acid are particularly preferable from the viewpoint of crack resistance. Isobutyl acid, t-butyl (meth) acrylate, 21-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , (Meta) glycidyl acrylate, (meth) furfuryl acrylate, tetrahydrofurfuryl (meth) acrylate and the like are more preferable.
　共重合体Ａ中の単量体（ａ）は、５～７５質量％が好ましく、３０～６０質量％が更に好ましい。 The monomer (a) in the copolymer A is preferably 5 to 75% by mass, more preferably 30 to 60% by mass.
　単量体（ａ）の含有量は、具体的には例えば、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０、６５、７０、７５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 Specifically, the content of the monomer (a) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75% by mass. , It may be within the range between any two of the numerical values exemplified here.
　前記範囲内の共重合体Ａを本発明の塗料組成物として使用した場合、特に塗膜溶解性が良好となる。 When the copolymer A within the above range is used as the coating composition of the present invention, the coating film solubility is particularly good.
　共重合体Ａの重量平均分子量（Ｍｗ）は５０００～３０００００であることが望ましい。分子量が５０００未満であれば、防汚塗料の塗膜が脆弱となり、剥離やクラックを起こし易く、また、３０００００を超えると、重合体溶液の粘度が上昇し、取扱いが困難となるからである。このＭｗは、具体的には例えば、５０００、１００００、２００００、３００００、４００００、５００００、６００００、７００００、８００００、９００００、１０００００、２０００００、３０００００であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 It is desirable that the weight average molecular weight (Mw) of the copolymer A is 5000 to 300,000. This is because if the molecular weight is less than 5,000, the coating film of the antifouling paint becomes fragile and easily peels or cracks, and if it exceeds 300,000, the viscosity of the polymer solution increases, making handling difficult. Specifically, this Mw is, for example, 5000, 10000, 20000, 30000, 40,000, 50000, 60000, 70000, 80000, 90000, 100000, 200,000, 300,000, and is between any two of the numerical values exemplified here. It may be within the range.
　Ｍｗの測定方法としては、例えばゲル浸透クロマトグラフィー（ＧＰＣ法）が挙げられる。 Examples of the method for measuring Mw include gel permeation chromatography (GPC method).
　共重合体Ａは、単量体（ａ）と単量体（ｂ）とのランダム共重合体、交互共重合体、周期的共重合体、又はブロック共重合体のいずれの共重合体であってもよい。 The copolymer A is a copolymer of a random copolymer of a monomer (a) and a monomer (b), an alternating copolymer, a periodic copolymer, or a block copolymer. You may.
　共重合体Ａは、例えば、重合開始剤の存在下、単量体（ａ）及び単量体（ｂ）を重合させることにより得ることができる。 The copolymer A can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.
　前記重合開始剤としては、例えば、２，２'－アゾビスイソブチロニトリル、２，２'－アゾビス（２－メチルブチロニトリル）、２，２'－アゾビス（２，４－ジメチルバレロニトリル）、ジメチル－２，２'－アゾビスイソブチレート、ジメチル２，２'－アゾビスイソブチレート、２，２'－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミド等のアゾ化合物；ベンゾイルパーオキサイド、ジ－ｔｅｒｔ－ブチルパーオキサイド、ｔｅｒｔ－ブチルパーオキシベンゾエート、ｔｅｒｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキサノエイト、ｔ－ヘキシルパーオキシ－２－エチルヘキサノエイト、ジ－ｔ－ヘキシルパーオキサイド、ｔ－ブチルパーオキシ－２－エチルヘキシルモノカルボネート、ジ－ｔ－ブチルパーオキサイド、１，１，３，３－テトラメチルブチルパーオキシネオデカノエート、ｔ－アミルパーオキシネオデカノエート、ｔ－ヘキシルパーオキシピバレート、ｔ－アミルパーオキシピバレート、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエイト等の過酸化物等が挙げられる。これら重合開始剤は、単独又は２種以上を組み合わせて使用できる。前記重合開始剤としては、特に、２，２'－アゾビスイソブチロニトリル、２，２'－アゾビス（２－メチルブチロニトリル）、２，２'－アゾビス（２，４－ジメチルバレロニトリル）、ジメチル２，２'－アゾビスイソブチレート及び１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエイトが好ましい。重合開始剤の使用量を適宜設定することにより、共共重合体Ａの分子量を調整することができる。 Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2,4-dimethylvaleronitrile). ), Dimethyl-2,2'-azobisisobutyrate, dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (N-butyl-2-methylpropionamide and other azo compounds; benzoylper Oxide, di-tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , Di-t-hexyl peroxide, t-butylperoxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t- Amilperoxyneodecanoate, t-hexylperoxypivalate, t-amylperoxypivalate, peroxides such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, etc. These polymerization initiators can be used alone or in combination of two or more. The polymerization initiators include, in particular, 2,2'-azobisisobutyronitrile and 2,2'-azobis (2). -Methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate is preferable. The molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.
　重合方法としては、例えば、溶液重合、塊状重合、乳化重合、懸濁重合、非水分散重合等が挙げられる。この中でも特に、簡便に、且つ、精度良く、共重合体Ａを得ることができる点で、溶液重合、又は非水分散重合が好ましい。 Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, non-aqueous dispersion polymerization and the like. Of these, solution polymerization or non-aqueous dispersion polymerization is particularly preferable in that copolymer A can be obtained easily and accurately.
　前記重合反応においては、必要に応じて有機溶媒を用いてもよい。有機溶剤としては、特に限定されないが、例えば、キシレン、トルエン等の芳香族炭化水素系溶剤；脂肪族炭化水素系溶剤；酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸メトキシプロピル等のエステル系溶剤；イソプロピルアルコール、ブチルアルコール、プロピレングリコールモノメチルエーテル等のアルコール系溶剤；ジオキサン、ジエチルエーテル、ジブチルエーテル等のエーテル系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤等が挙げられる。
　その中でも、酢酸ブチル、酢酸イソブチル、ブチルアルコール、プロピレングリコールモノメチルエーテル、プロピレングリコール1-モノメチルエーテル2-アセタート、トルエン、キシレンが好ましい。これら溶媒については、単独あるいは２種以上を組み合わせて使用できる。 In the polymerization reaction, an organic solvent may be used if necessary. The organic solvent is not particularly limited, but for example, an aromatic hydrocarbon solvent such as xylene and toluene; an aliphatic hydrocarbon solvent; an ester solvent such as ethyl acetate, butyl acetate, isobutyl acetate and methoxypropyl acetate; isopropyl. Alcohol-based solvents such as alcohol, butyl alcohol and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be mentioned.
Among them, butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene and xylene are preferable. These solvents can be used alone or in combination of two or more.
　重合反応における反応温度は、重合開始剤の種類等に応じて適宜設定すればよく、通常５０～１６０℃であり、好ましくは６０～１５０℃である。 The reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually 50 to 160 ° C, preferably 60 to 150 ° C.
　重合反応は、窒素ガス、アルゴンガス等の不活性ガス雰囲気下で行われることが好ましい。 The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
１－１－２．オルガノポリシロキサンＢ
　オルガノポリシロキサンＢは、架橋反応性官能基を有するオルガノポリシロキサンである。架橋反応性官能基は、分子鎖中のケイ素原子上に有することが好ましい。また、架橋反応性官能基以外の有機基を有することが好ましい。 1-1-2. Organopolysiloxane B
Organopolysiloxane B is an organopolysiloxane having a cross-linking reactive functional group. The crosslinkable functional group is preferably provided on a silicon atom in the molecular chain. Moreover, it is preferable to have an organic group other than the cross-linking reactive functional group.
　上記架橋反応性官能基としては、例えば、水酸基、メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基；ベンジルオキシ基などのアラルキルオキシ基等が挙げられる。 Examples of the cross-linking reactive functional group include an alkoxy group such as a hydroxyl group, a methoxy group, an ethoxy group and a propoxy group; and an aralkyloxy group such as a benzyloxy group.
　上記有機基としては、オルガノポリシロキサンが一般的に有する有機基が挙げられ、具体的にはメチル基、エチル基、プロピル基などのアルキル基；シクロペンチル基、シクロヘキシル基などのシクロアルキル基；ビニル基、アリル基などのアルケニル基；ベンジル基などのアラルキル基；フェニル基、ナフチル基などのアリール基；３，３，３－トリフルオロプロピル基などのハロゲン化アルキル基などが挙げられる。 Examples of the organic group include organic groups generally possessed by organopolysiloxane, and specifically, alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl group. , Alkenyl group such as allyl group; aralkyl group such as benzyl group; aryl group such as phenyl group and naphthyl group; alkyl halide group such as 3,3,3-trifluoropropyl group and the like.
　オルガノポリシロキサンＢは、触媒の存在下で、且つ水分（空気中の水分であってもよい）の存在下、縮合反応してオルガノポリシロキサンゴムを形成する。具体的に、上記オルガノポリシロキサンＢ中の架橋反応性官能基が、他のオルガノポリシロキサンＢの架橋反応性官能基や架橋剤中の加水分解性基と縮合反応することによりシリコーンゴムを形成し、被膜となる。 Organopolysiloxane B forms an organopolysiloxane rubber by a condensation reaction in the presence of a catalyst and in the presence of moisture (which may be moisture in the air). Specifically, the cross-linking reactive functional group in the organopolysiloxane B forms a silicone rubber by condensation reaction with the cross-linking reactive functional group of another organopolysiloxane B or the hydrolyzable group in the cross-linking agent. , Becomes a film.
　かかる縮合反応における反応温度は、通常８０℃以下、好ましくは５０℃以下である。 The reaction temperature in such a condensation reaction is usually 80 ° C. or lower, preferably 50 ° C. or lower.
　オルガノポリシロキサンＢの重量平均分子量は、４００～１００００００が好ましく、２０００～１５００００がより好ましく、４０００～８００００がさらに好ましい。異なる重量平均分子量のものを二種以上で併用して用いることもできる。この重量平均分子量は、具体的には例えば、４００、２０００、４０００、１００００、２００００、３００００、４００００、５００００、６００００、７００００、８００００、１０００００、１５００００、５０００００、１００００００であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The weight average molecular weight of the organopolysiloxane B is preferably 400 to 1,000,000, more preferably 2000 to 150,000, and even more preferably 4000 to 80,000. Two or more kinds having different weight average molecular weights can be used in combination. Specifically, the weight average molecular weight is, for example, 400, 2000, 4000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 100000, 150,000, 500000, 1000000, and the numerical values exemplified here are used. It may be within the range between any two.
　オルガノポリシロキサンＢの市販品としては、ＲＦ―５０００、ＲＦ－１００００（以上、信越化学工業社製）、ＸＩＡＭＥＴＥＲ　ＯＨＸ－４０１０　Ｐｏｌｙｍｅｒ、ＸＩＡＭＥＴＥＲ　ＯＨＸ－４０１２　Ｐｏｌｙｍｅｒ（以上、ダウ・コーニング社製）、ＸＣ９６－７２３、ＹＦ３８００、ＸＦ３９０５、ＹＦ３０５７、ＹＦ３８０７、ＹＦ３８０２、ＹＦ３８９７、ＹＲ３２０４（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＢＬＵＥＳＩＬ　ＦＬＤ　４８Ｖ３５００（以上、エルケム社製）、ＰＯＬＹＭＥＲ　ＦＤ　６（ワッカー・ケミー社製）、ＤＭＳ－Ｓ２１、ＤＭＳ－Ｓ２７、ＤＭＳ－Ｓ３１、ＤＭＳ－Ｓ３２、ＤＭＳ－Ｓ３３、ＤＭＳ－Ｓ３５、ＤＭＳ－Ｓ４２、ＤＭＳ－Ｓ４５、ＤＭＳ－Ｓ５１、ＰＤＳ－０３３２、ＰＤＳ－９９３１、ＦＭＳ－９９２２（Ｇｅｌｅｓｔ社製）等が挙げられる。 Commercially available products of organopolysiloxane B include RF-5000, RF-10000 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), XIAMETER OHG-4010 Polymer, XIAMETER OHG-4012 Polymer (above, manufactured by Dow Corning), XC96- 723, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, YR3204 (above, Momentive Performance Materials), BLUESIL FLD 48V3500 (above, Elchem), POLYMER FD 6 (Wacker Chemie), DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-9931, FMS-9922 (Gelest) Made) and the like.
１－２．焼成カオリン
　焼成カオリンは、熱的な方法によって天然に産出する含水カオリン（理論的な組成［Ａｌ２Ｓｉ２Ｏ５（ＯＨ）４］をもつ含水アルミノケイ酸塩のカオリナイト）から脱ヒドロキシル化された形に変換されたカオリンをいう。焼成は、その他の特性の中でカオリン構造を結晶形から非晶質形に変化させる。焼成は、例えば５００℃～１２００℃の範囲の温度、例えば８００℃～１２００℃の範囲の温度で、いずれかの既知の方法で、きめの粗いまたは細かな含水カオリンを加熱処理することによって実行される。 1-2. Calcined Kaolin Calcined kaolin was dehydroxylated from naturally occurring hydrous kaolin (kaolinite, a hydrous aluminosilicate with a theoretical composition [Al 2 Si 2 O 5 (OH) 4 ]) that is naturally produced by thermal methods. Kaolin transformed into a form. Firing changes the kaolin structure from crystalline to amorphous, among other properties. The calcination is carried out by heat-treating the coarse or fine hydrous kaolin, for example at a temperature in the range of 500 ° C. to 1200 ° C., for example, at a temperature in the range of 800 ° C. to 1200 ° C., by any known method. To.
　前記焼成カオリンとしては、市販品として、例えば、Ｔｒａｎｓｌｉｎｋ４４５（ＢＡＳＦ社製）、ＳａｔｉｎｔｏｎｅＷ、Ｓａｔｉｎｔｏｎｅ５、Ｓａｔｉｎｔｏｎｅ５ＨＢ（ＢＡＳＦ Ｃｏｒｐｏｒａｔｉｏｎ製）等が挙げられる。 Examples of the commercially available calcined kaolin include Translink 445 (manufactured by BASF), Satintone W, Satintone 5, and Satintone 5HB (manufactured by BASF Corporation).
　前記焼成カオリンの白色度は７５％以上のものが好ましく、８０％以上のものが更に好ましい。白色度はＩＳＯ２４６９で定められた測定方法で測定される。 The whiteness of the calcined kaolin is preferably 75% or more, and more preferably 80% or more. Whiteness is measured by the measuring method defined by ISO2469.
　前記焼成カオリンの平均粒径は、０．１～５．０μｍが好ましく、０．４～２．０μｍが更に好ましい。平均粒径は、例えばＭｉｃｒｏｍｅｒｉｔｉｃｓ（Ａｔｌａｎｔａ，Ｇａ）製のＳｅｄｉｇｒａｐｈ（登録商標）５１００粒径分析装置を使用して、水性媒体中の完全に分散された状態での粒子物質の沈降法による既知の方法で測定される。この平均粒子径は、具体的には例えば、０．１、０．２、０．３、０．４、０．５、０．６、０．７、０．８、０．９、１．０、１．１、１．２、１．３、１．４、１．５、１．６、１．７、１．８、１．９、２．０、３．０、４．０、５．０であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The average particle size of the calcined kaolin is preferably 0.1 to 5.0 μm, more preferably 0.4 to 2.0 μm. The average particle size is determined by, for example, a known method of sedimentation of particulate matter in a fully dispersed state in an aqueous medium using a Sedigraf® 5100 particle size analyzer manufactured by Micromeritics (Atlanta, Ga). Measured at. Specifically, the average particle size is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1. 0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 3.0, 4.0, It is 5.0 and may be in the range between any two of the numerical values exemplified here.
　本発明の組成物中における焼成カオリンの含有量は特に制限されないが、固形分換算で、通常１～４０質量％であり、好ましくは５～２０質量％である。焼成カオリンを前記範囲内で使用した場合、特に耐候性試験後の浸漬試験における防汚性能が著しく良好となる。焼成カオリンの含有量は、具体的には例えば、１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０、２５、３０、３５、４０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The content of calcined kaolin in the composition of the present invention is not particularly limited, but is usually 1 to 40% by mass, preferably 5 to 20% by mass in terms of solid content. When calcined kaolin is used within the above range, the antifouling performance is remarkably improved particularly in the immersion test after the weather resistance test. Specifically, the content of calcined kaolin is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 , 20, 25, 30, 35, 40% by mass, and may be within the range between any two of the numerical values exemplified here.
１－３．防汚薬剤
　防汚薬剤としては、例えば無機薬剤及び有機薬剤が挙げられる。 1-3. Antifouling agents Examples of antifouling agents include inorganic agents and organic agents.
　無機薬剤としては、例えば、亜酸化銅、チオシアン酸銅（一般名：ロダン銅）、銅粉等が挙げられる。この中でも特に、亜酸化銅とロダン銅が好ましく、亜酸化銅はグリセリン、ショ糖、ステアリン酸、ラウリン酸、リシチン、鉱物油などで表面処理されているものが、貯蔵時の長期安定性の点でより好ましい。 Examples of the inorganic drug include cuprous oxide, copper thiocyanate (generic name: copper rodan), copper powder and the like. Of these, copper cuprous oxide and copper rodane are particularly preferable, and copper cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, ricitin, mineral oil, etc., has long-term stability during storage. Is more preferable.
　有機薬剤としては、例えば、２－メルカプトピリジン－Ｎ－オキシド銅（一般名：カッパーピリチオン）、２－メルカプトピリジン－Ｎ－オキシド亜鉛（一般名：ジンクピリチオン）、ジンクエチレンビスジチオカーバメート（一般名：ジネブ）、４，５－ジクロロ－２－ｎ－オクチル－３－イソチアゾロン（一般名：シーナイン２１１）、３，４－ジクロロフェニル－Ｎ－Ｎ－ジメチルウレア（一般名：ジウロン）、２－メチルチオ－４－ｔ－ブチルアミノ－６－シクロプロピルアミノ－ｓ－トリアジン（一般名：イルガロール１０５１）、２－（ｐ－クロロフェニル）－３－シアノ－４－ブロモ－５－トリフルオロメチルピロール（一般名：Ｅｃｏｎｅａ２８）、４－［１－（２，３－ジメチルフェニル）エチル］－１Ｈ－イミダゾール（一般名：メデトミジン）等が挙げられる。 Examples of organic agents include 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-zinc oxide (generic name: zinc pyrithione), and zinc ethylenebisdithiocarbamate (generic name: dineb). ), 4,5-Dichloro-2-n-octyl-3-isothiazolone (generic name: cinine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diuron), 2-methylthio-4- t-Butylamino-6-cyclopropylamino-s-triazine (generic name: irgalol 1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28) , 4- [1- (2,3-Dimethylphenyl) ethyl] -1H-imidazole (generic name: medetomidin) and the like.
　これらの防汚薬剤のうち、耐候性試験後の浸漬試験における防汚性能の観点から特に２－（ｐ－クロロフェニル）－３－シアノ－４－ブロモ－５－トリフルオロメチルピロール（一般名：Ｅｃｏｎｅａ２８）が好ましい。これらの防汚薬剤は１種又は２種以上併用して使用できる。 Among these antifouling agents, 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28) is particularly effective from the viewpoint of antifouling performance in the immersion test after the weather resistance test. ) Is preferable. These antifouling agents can be used alone or in combination of two or more.
　本発明の組成物中における防汚薬剤の含有量は特に制限されないが、固形分換算で、通常０．１～６０質量％であり、好ましくは１～５０質量％である。防汚薬剤の含有量は、具体的には例えば、０．１、１、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 60% by mass, preferably 1 to 50% by mass in terms of solid content. Specifically, the content of the antifouling agent is, for example, 0.1, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass, and here. It may be in the range between any two of the illustrated values.
１－４．他の添加剤
　さらに本発明の防汚塗料用樹脂には、必要に応じて、他の添加剤を添加してもいい。樹脂成分Ｒが共重合体Ａである場合には、他の添加剤としては、共重合体Ａ以外の樹脂成分、溶出調整剤、可塑剤、顔料、染料、消泡剤、脱水剤、揺変剤、有機溶剤等が挙げられる。樹脂成分ＲがオルガノポリシロキサンＢである場合には、他の添加剤としては、可塑剤、顔料、染料、消泡剤、充填剤、脱水剤、揺変剤、架橋剤、縮合触媒、ブリードオイル、有機溶剤等が挙げられる。 1-4. Other Additives Further, other additives may be added to the antifouling paint resin of the present invention, if necessary. When the resin component R is the copolymer A, the other additives include a resin component other than the copolymer A, an elution adjuster, a plasticizer, a pigment, a dye, a defoaming agent, a dehydrating agent, and shaking. Examples include agents and organic solvents. When the resin component R is organopolysiloxane B, other additives include plasticizers, pigments, dyes, defoamers, fillers, dehydrators, shakers, crosslinkers, condensation catalysts, and bleed oils. , Organic solvent and the like.
　他の樹脂成分としては、例えば、重合体Ｐなどが挙げられる。
　重合体Ｐは、前記単量体（ｂ）を重合することにより得られる重合体である。単量体（ｂ）は、単量体（ａ）以外の任意のエチレン性不飽和単量体である。重合体Ｐの重合に用いる単量体（ｂ）は、共重合体Ａの重合に用いる単量体（ｂ）と同一の組成であっても異なる組成であってもよい。
　本発明においては、単量体（ｂ）を単独又は二種以上で用いることができ、特に、共重合体Ａとの相溶性の観点から、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸２一エチルヘキシル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸フルフリル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸ベンジルが好ましい。
　重合方法、開始剤、溶媒、温度、その他の条件、Ｍｗの測定方法等は、共重合体Ａで既記の手法が適用できる。
　本発明の組成物中における重合体Ｐの含有量は特に制限されないが、共重合体Ａとの含有割合が、固形分換算で、質量比（重合体Ｐ／共重合体Ａ）は、通常０．１～９．０であり、好ましくは０．１～４．０である。 Examples of other resin components include polymer P and the like.
The polymer P is a polymer obtained by polymerizing the monomer (b). The monomer (b) is any ethylenically unsaturated monomer other than the monomer (a). The monomer (b) used for the polymerization of the polymer P may have the same composition as or different from the monomer (b) used for the polymerization of the copolymer A.
In the present invention, the monomer (b) can be used alone or in combination of two or more, and in particular, from the viewpoint of compatibility with the copolymer A, methyl (meth) acrylate and ethyl (meth) acrylate. , (Meta) butyl acrylate, (meth) acrylate isobutyl, (meth) acrylate t-butyl, (meth) acrylate 21-ethylhexyl, (meth) acrylate 2-methoxyethyl, (meth) acrylate 2- Ethoxyethyl, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and benzyl (meth) acrylate are preferred.
As the polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, etc., the method described above for copolymer A can be applied.
The content of the polymer P in the composition of the present invention is not particularly limited, but the content ratio with the copolymer A is usually 0 in terms of solid content and the mass ratio (polymer P / copolymer A). It is .1 to 9.0, preferably 0.1 to 4.0.
　前記溶出調整剤としては、例えば、ロジン、ロジン誘導体、ナフテン酸、シクロアルケニルカルボン酸、ビシクロアルケニルカルボン酸、バーサチック酸、トリメチルイソブテニルシクロヘキセンカルボン酸、及びこれらの金属塩等の、モノカルボン酸及びその塩、又は前記脂環式炭化水素樹脂が挙げられる。これらは単独又は２種以上で使用できる。
　前記ロジン誘導体としては、水添ロジン、不均化ロジン、マレイン化ロジン、ホルミル化ロジン、重合ロジン等を例示できる。
　前記脂環式炭化水素樹脂としては、市販品として、例えば、クイントン１５００、１５２５Ｌ、１７００（商品名、日本ゼオン社製）等が挙げられる。
　この中でもロジン、ロジン誘導体、ナフテン酸、バーサチック酸、トリメチルイソブテニルシクロヘキセンカルボン酸、又はこれらの金属塩が好ましく、ロジン、ロジン誘導体が更に好ましい。
　ロジン、ロジン誘導体を使用することにより、塗膜の耐剥離性の向上性、および塗膜溶解性（特に初期段階における）の向上性が顕著となる。 Examples of the elution adjuster include monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof. Examples thereof include the salt thereof or the alicyclic hydrocarbon resin. These can be used alone or in combination of two or more.
Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
Examples of the commercially available alicyclic hydrocarbon resin include Quinton 1500, 1525L, 1700 (trade name, manufactured by Zeon Corporation).
Among these, rosin, rosin derivative, naphthenic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, or metal salts thereof are preferable, and rosin and rosin derivative are more preferable.
By using the rosin and the rosin derivative, the peeling resistance of the coating film and the solubility of the coating film (particularly in the initial stage) are remarkably improved.
　前記可塑剤としては、例えば、燐酸エステテル類、フタル酸エステル類、アジピン酸エステル類、セバシン酸エステル類、エポキシ化大豆油、アルキルビニルエーテル重合体、ポリアルキレングリコール類、ｔ－ノニルペンタスルフィド、ワセリン、ポリブテン、トリメリット酸トリス（２－エチルヘキシル）、シリコーンオイル、塩素化パラフィン等が挙げられる。これらは単独又は２種以上で使用できる。 Examples of the plasticizer include phosphoric acid esthetics, phthalates, adipates, sebacic acid esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, and vaseline. Examples thereof include polybutene, tristrimellitic acid (2-ethylhexyl), silicone oil, and chlorinated paraffin. These can be used alone or in combination of two or more.
　前記脱水剤としては、例えば、硫酸カルシウム、合成ゼオライト系吸着剤、オルソエステル類、テトラメトキシシラン、テトラエトキシシラン等のシリケート類やイソシアネート類、カルボジイミド類、カルボジイミダゾール類等が挙げられる。これらは単独または２種以上を組み合わせて使用することができる。 Examples of the dehydrating agent include calcium sulfate, synthetic zeolite-based adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbodiimidazoles. These can be used alone or in combination of two or more.
　充填剤としては、無機質充填剤及び／又は有機質充填剤が挙げられる。無機質充填剤としては例えば、炭酸カルシウム、沈降性硫酸バリウム、バライト粉、酸化チタン、けいそう土、水酸化アルミニウム、微粒状アルミナ、酸化マグネシウム、炭酸マグネシウム、タルク、ゼオライト、ベントナイト、シリカ粉末、フタロシアニンブルー、カーボンブラック等が挙げられる。有機質充填剤としては例えば、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、アクリルシリコーンなどの合成樹脂粉末等が挙げられる。
　揺変剤としては、脂肪酸アマイド、酸化ポリエチレン、シリカ、フュームドシリカ等が挙げられる。これらは単独または２種以上を組み合わせて使用することができる。 Examples of the filler include an inorganic filler and / or an organic filler. Examples of the inorganic filler include calcium carbonate, precipitated barium sulfate, barite powder, titanium oxide, silica soil, aluminum hydroxide, fine granular alumina, magnesium oxide, magnesium carbonate, talc, zeolite, bentonite, silica powder, and phthalocyanine blue. , Carbon black and the like. Examples of the organic filler include synthetic resin powders such as polypropylene, polyvinyl chloride, polystyrene, and acrylic silicone.
Examples of the rocking agent include fatty acid amide, polyethylene oxide, silica, fumed silica and the like. These can be used alone or in combination of two or more.
　架橋剤としては、ジアセトキシメチルシラン、ジアセトキシジメチルシラン、ジアセトキシメチルビニルシラン、メチルトリアセトキシシラン、トリアセトキシビニルシラン、テトラアセトキシシラン、エチルトリアセトキシシラン、ジアセトキシメチルフェニルシラン等のアセトキシ基を有するアセトキシシラン、メチルトリ（ブタノキシム）シラン、ビニルトリ（ブタノキシム）シラン、フェニルトリ（ブタノキシム）シラン、プロピルトリ（ブタノキシム）シラン等のケトオキシム基を有するシラン、メチルトリイソプロペノキシシラン、トリイソプロペノキシシラン、テトラプロペノキシシラン、フェニルトリアルケノキシシラン、イソプロピルプロペノキシシラン、ブチルトリプロペノキシシラン、ビニルトリプロペノキシシラン等のアルケノキシ基を有するシランなどが挙げられ、これらの１種を単独で又は２種以上を組み合わせて使用することができる。 Examples of the cross-linking agent include acetoxy having an acetoxy group such as diacetoxymethylsilane, diacetoxydimethylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane, triacetoxyvinylsilane, tetraacetoxysilane, ethyltriacetoxysilane, and diacetoxymethylphenylsilane. Silanes having ketooxime groups such as silane, methyltri (butanoxime) silane, vinyltri (butanoxime) silane, phenyltri (butanoxime) silane, propyltri (butanoxime) silane, methyltriisopropenoxysilane, triisopropenoxysilane, tetraprope Examples thereof include silanes having an alkenoxy group such as noxysilane, phenyltrialkenoxysilane, isopropylpropenoxysilane, butyltripropenoxysilane, and vinyltripropenoxysilane, and one of these may be used alone or in combination of two or more. Can be used in combination.
　縮合触媒としては、ジブチルスズジアセテート等の有機スズ化合物、テトライソプロピルチタネート等の有機チタン化合物、などが挙げられ、これらの１種を単独で又は２種以上を組み合わせて使用することができる。 Examples of the condensation catalyst include an organic tin compound such as dibutyltin diacetate and an organic titanium compound such as tetraisopropyl titanate, and one of these can be used alone or in combination of two or more.
　ブリードオイルとしては、具体的には、シリコーンオイル、アクリルポリマーとジメチルポリシロキサンからなるグラフト共重合体、パーフルオロポリエーテルオイル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンひまし油、ポリオキシエチレン硬化ひまし油などが挙げられる。これら化合物は一種単独でまたは二種以上を組み合わせて使用できる。 Specific examples of the bleed oil include silicone oil, a graft copolymer composed of an acrylic polymer and dimethylpolysiloxane, perfluoropolyether oil, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and poly. Examples thereof include oxyethylene castor oil and polyoxyethylene cured castor oil. These compounds can be used alone or in combination of two or more.
　ブリードオイルは、上記オルガノポリシロキサンＢの縮合反応により形成されるオルガノポリシロキサンゴムとの相溶性に優れる。そのため、本発明の組成物によれば、剥離等の生じにくい塗膜性能に優れた塗膜を好適に形成できる。 The bleed oil has excellent compatibility with the organopolysiloxane rubber formed by the condensation reaction of the organopolysiloxane B. Therefore, according to the composition of the present invention, it is possible to suitably form a coating film having excellent coating film performance in which peeling and the like are unlikely to occur.
　有機溶剤としては、例えば、キシレン、トルエン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、酢酸ブチル、メタノール、エタノール、プロパノール、イソプロピルアルコール、イソアミルアルコール、ｎ－ブタノール、１－メトキシ－２－プロパノール、グリコール系エステル、芳香族炭化水素、脂肪族系炭化水素、ホワイトスピリット、脂環式炭化水素系溶剤、ナフテン系炭化水素、ミネラルスピリット、脂肪族ソルベントナフサ、低沸点芳香族ナフサ、イソパラフィン、ノルマルパラフィン等が挙げられる。
これら有機溶剤は、単独でまたは２種以上を混合して用いることができる。 Examples of the organic solvent include xylene, toluene, hexane, heptane, octane, cyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, butyl acetate, methanol, ethanol, propanol, isopropyl alcohol, isoamyl alcohol, n-butanol, 1 -Methoxy-2-propanol, glycol-based ester, aromatic hydrocarbon, aliphatic hydrocarbon, white spirit, alicyclic hydrocarbon-based solvent, naphthenic hydrocarbon, mineral spirit, aliphatic solvent naphtha, low boiling point aromatic Examples include naphtha, isoparaffin, normal paraffin and the like.
These organic solvents can be used alone or in combination of two or more.
２．防汚塗料組成物の製造方法
　本発明の防汚塗料組成物は、例えば、樹脂成分Ｒ及び焼成カオリン、他の添加剤等を含有する混合液を、分散機を用いて混合分散することにより製造できる。また、樹脂成分Ｒ及び防汚薬剤、他の添加剤等を含有する混合液を、分散機を用いて混合分散した後に、焼成カオリンを添加して製造することもできる。
　前記混合液としては、樹脂成分Ｒ及び焼成カオリン等の各種材料を溶媒に溶解または分散させたものであることが好ましい。前記溶媒としては、上記有機溶媒と同様のものを使用できる。
　前記分散機としては、例えば、微粉砕機として使用できるものを好適に用いることができる。例えば、市販のホモミキサー、サンドミル、ビーズミル、ディスパー、ペイントシェーカー等を使用することができる。また、撹拌機を備えた容器に混合分散用のガラスビーズ等を加えたものを用い、前記混合液を混合分散してもよい。
　本発明の防汚塗料組成物は、一液構成であっても複数液（例えば二液）構成であってもよい。樹脂成分ＲがオルガノポリシロキサンＢである場合、複数液構成とし、縮合触媒と架橋剤の少なくとも一方を、オルガノポリシロキサンＢとは別の液に配合した上で、塗料として利用する直前に混合することが好ましい。これによって、貯蔵安定性が向上する。 2. Method for Producing Antifouling Paint Composition The antifouling coating composition of the present invention is produced by mixing and dispersing, for example, a mixed solution containing resin component R, calcined kaolin, other additives, etc. using a disperser. it can. It is also possible to produce by adding calcined kaolin after mixing and dispersing a mixed solution containing the resin component R, an antifouling agent, other additives and the like using a disperser.
The mixed solution is preferably one in which various materials such as resin component R and calcined kaolin are dissolved or dispersed in a solvent. As the solvent, the same solvent as the above organic solvent can be used.
As the disperser, for example, one that can be used as a fine pulverizer can be preferably used. For example, a commercially available homomixer, sand mill, bead mill, disper, paint shaker or the like can be used. Further, the mixed solution may be mixed and dispersed by using a container provided with a stirrer to which glass beads or the like for mixing and dispersing are added.
The antifouling coating composition of the present invention may be composed of one liquid or a plurality of liquids (for example, two liquids). When the resin component R is an organopolysiloxane B, a plurality of liquids are formed, and at least one of the condensation catalyst and the cross-linking agent is mixed in a liquid different from the organopolysiloxane B and then mixed immediately before use as a paint. Is preferable. This improves storage stability.
３．防汚処理方法、防汚塗膜、および塗装物
　本発明の防汚処理方法は、上記防汚塗料組成物を用いて被塗膜形成物の表面に防汚塗膜を形成する。本発明の防汚処理方法によれば、前記防汚塗膜が表面から徐々に溶解し塗膜表面が常に更新されることにより、水棲汚損生物の付着防止を図ることができる。
　被塗膜形成物としては、例えば、船舶（特に船底）、漁業具、水中構造物等が挙げられる。
　防汚塗膜の厚みは、被塗膜形成物の種類、船舶の航行速度、海水温度等に応じて適宜設定すればよい。例えば、被塗膜形成物が船舶の船底の場合、防汚塗膜の厚みは通常５０～７００μｍ、好ましくは１００～６００μｍである。 3. 3. Antifouling treatment method, antifouling coating film, and coated material In the antifouling treatment method of the present invention, an antifouling coating film is formed on the surface of the coating film to be formed using the above antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film is gradually dissolved from the surface and the surface of the coating film is constantly updated, so that adhesion of aquatic polluted organisms can be prevented.
Examples of the coating film-forming product include ships (particularly the bottom of ships), fishing gear, underwater structures, and the like.
The thickness of the antifouling coating film may be appropriately set according to the type of the coating film to be formed, the navigation speed of the ship, the seawater temperature, and the like. For example, when the coating film to be formed is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 700 μm, preferably 100 to 600 μm.
　以下に、実施例等を示し本発明の特徴とするところをより一層明確にする。ただし、本発明は実施例等に限定されるものではない。
　各製造例、実施例及び比較例中の％は質量％を示す。重量平均分子量（Ｍｗ）は、ＧＰＣにより求めた値（ポリスチレン換算値）である。ＧＰＣの条件は下記の通りである。
装置・・・　東ソー株式会社製　ＨＬＣ－８２２０ＧＰＣ
カラム・・・　ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｍ　　２本
流量・・・　０．３５ｍＬ／ｍｉｎ
検出器・・・　ＲＩ
カラム恒温槽温度・・・　４０℃
溶離液・・・　ＴＨＦ
加熱残分は、ＪＩＳ　Ｋ　５６０１－１－２：１９９９（ＩＳＯ　３２５１：１９９３）「塗料成分試験方法－加熱残分」に準拠して測定した値である。 Examples and the like are shown below to further clarify the features of the present invention. However, the present invention is not limited to the examples and the like.
% In each production example, example and comparative example indicates mass%. The weight average molecular weight (Mw) is a value (polystyrene conversion value) obtained by GPC. The conditions of GPC are as follows.
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column ・ ・ ・ TSKgel SuperHZM-M 2 flow rate ・ ・ ・ 0.35mL / min
Detector ・ ・ ・ RI
Column constant temperature bath temperature ・ ・ ・ 40 ℃
Eluent ・ ・ ・ THF
The heating residue is a value measured in accordance with JIS K 5601-1-2: 1999 (ISO 3251: 1993) "Paint component test method-heating residue".
１．製造例
＜製造例１（共重合体溶液Ａ１の製造）＞
　温度計、冷却器、攪拌装置及び滴下ロートを備えた四ツ口フラスコに、キシレン６０ｇ（初期溶媒）を仕込み、窒素ガスを導入し、攪拌しながら８８℃を保持した。そこへ、メタクリル酸トリイソプロピルシリル３０ｇ、アクリル酸テトラヒドロフルフリル３ｇ、アクリル酸２－メトキシエチル９ｇ、メタクリル酸２－メトキシエチル２５ｇ、メクリル酸メチル２８ｇ、アクリル酸ｎ－ブチル３ｇ、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエイト０．８ｇ（初期添加）の混合液を８８℃で保持しながら３時間かけて滴下した。その後、８８℃で１時間攪拌を行った後、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエイト０．１ｇ（後添加）を１時間毎に３回添加し、さらに同温度で２時間攪拌を行った後、キシレン４０ｇ（希釈溶媒）添加し室温に冷却し、共重合体Ａを含む共重合体溶液Ａ１を得た。共重合体溶液Ａ１の加熱残分およびＭｗを表１に示す。 1. 1. Production Example <Production Example 1 (Production of copolymer solution A1)>
60 g (initial solvent) of xylene was charged into a four-necked flask equipped with a thermometer, a cooler, a stirrer and a dropping funnel, nitrogen gas was introduced, and the temperature was maintained at 88 ° C. while stirring. There, 30 g of triisopropylsilyl methacrylate, 3 g of tetrahydrofurfuryl acrylate, 9 g of 2-methoxyethyl acrylate, 25 g of 2-methoxyethyl methacrylate, 28 g of methyl mecrylate, 3 g of n-butyl acrylate, 1,1,3 , 3-Tetramethylbutylperoxy-2-ethylhexanoate 0.8 g (initial addition) was added dropwise over 3 hours while maintaining at 88 ° C. Then, after stirring at 88 ° C. for 1 hour, 0.1 g (post-addition) of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added 3 times every hour. After further stirring at the same temperature for 2 hours, 40 g (diluting solvent) of xylene was added and the mixture was cooled to room temperature to obtain a copolymer solution A1 containing the copolymer A. The heating residue and Mw of the copolymer solution A1 are shown in Table 1.
＜製造例２～９（共重合体溶液Ａ２～Ａ７、重合体溶液Ｐ１～Ｐ２の製造）＞
　表１に示す単量体、重合開始剤及び溶媒を用いて、各反応温度条件下、製造例１と同様の操作で重合反応を行うことにより、共重合体Ａを含む共重合体溶液Ａ２～Ａ７、およびその他の重合体Ｐを含む重合体溶液Ｐ１～Ｐ２を得た。加熱残分およびＭｗを表１に示す。表中の数値は質量％である。 <Production Examples 2 to 9 (Production of Copolymer Solutions A2 to A7 and Polymer Solutions P1 to P2)>
The copolymer solutions A2 to contain the copolymer A by carrying out the polymerization reaction in the same manner as in Production Example 1 under each reaction temperature condition using the monomers, the polymerization initiator and the solvent shown in Table 1. Polymer solutions P1 to P2 containing A7 and other polymer P were obtained. The heating residue and Mw are shown in Table 1. The numerical value in the table is mass%.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表中の成分の詳細は、以下の通りである。
　ナフテゾール１６０：ＪＸＴＧエネルギー社製、ナフテン系溶剤 The details of the components in the table are as follows.
Naphthezol 160: Naphthenic solvent manufactured by JXTG Energy Co., Ltd.
＜製造例１０（ロジン亜鉛塩溶液の製造）＞
　温度計、還流冷却器、及び攪拌機を備えたフラスコに、中国産ガムロジン（ＷＷ）２４０ｇとキシレン３６０ｇをフラスコに入れ、更に、前記ロジン中の樹脂酸が全て亜鉛塩を形成するように酸化亜鉛１２０ｇを加え、７０～８０℃で３時間、減圧下で還流脱水した。その後、冷却しろ過を行うことにより、ロジン亜鉛塩のキシレン溶液（濃褐色透明液体、固形分５０％）を得た。得られた溶液の加熱残分は、５０．２％であった。 <Production Example 10 (Production of rosin zinc salt solution)>
In a flask equipped with a thermometer, a reflux condenser, and a stirrer, 240 g of Chinese gum rosin (WW) and 360 g of xylene are placed in the flask, and 120 g of zinc oxide is added so that all the resin acids in the rosin form zinc salts. Was added, and the mixture was reflux-dehydrated at 70 to 80 ° C. for 3 hours under reduced pressure. Then, it was cooled and filtered to obtain a xylene solution of rosin zinc salt (dark brown transparent liquid, solid content 50%). The heating residue of the obtained solution was 50.2%.
＜製造例１１（水添ロジン亜鉛塩溶液の製造）＞
　温度計、還流冷却器、及び攪拌機を備えたフラスコに、ハイペールＣＨ（水添ロジン）２４０ｇとキシレン３６０ｇをフラスコに入れ、更に、前記ロジン中の樹脂酸が全て亜鉛塩を形成するように酸化亜鉛１２０ｇを加え、７０～８０℃で３時間、減圧下で還流脱水した。その後、濃縮、冷却しろ過を行うことにより、水添ロジン亜鉛塩のキシレン溶液（濃褐色液体、固形分５０％）を得た。得られた溶液の加熱残分は、５０．３％であった。 <Production Example 11 (Production of Hydrogenated Rosin Zinc Salt Solution)>
In a flask equipped with a thermometer, a reflux condenser, and a stirrer, 240 g of hyper-CH (hydrogenated rosin) and 360 g of xylene are placed in the flask, and zinc oxide is further formed so that all the resin acids in the rosin form zinc salts. 120 g was added, and the mixture was reflux-dehydrated at 70-80 ° C. for 3 hours under reduced pressure. Then, it concentrated, cooled and filtered to obtain a xylene solution of hydrogenated rosin zinc salt (dark brown liquid, solid content 50%). The heating residue of the obtained solution was 50.3%.
２．実施例及び比較例（塗料組成物の製造）
　表２～表５に示す成分を当該表に示す割合（質量％）で配合し、直径１．５～２．５ｍｍのガラスビーズと混合分散することにより塗料組成物を製造した。なお、表５に示す実施例・比較例の防汚塗料組成物は、ａ成分を有するａ液と、ｂ成分を有するｂ液の二液構成とした。 2. Examples and Comparative Examples (Manufacturing of Paint Composition)
A coating composition was produced by blending the components shown in Tables 2 to 5 in the proportions (mass%) shown in the table and mixing and dispersing them with glass beads having a diameter of 1.5 to 2.5 mm. The antifouling coating composition of Examples and Comparative Examples shown in Table 5 had a two-component structure consisting of a liquid a having a component a and a liquid b having a component b.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表中の各成分の詳細は、以下の通りである。
＜焼成カオリン＞
　焼成カオリン：Ｔｒａｎｓｌｉｎｋ４４５（ＢＡＳＦ社製：白色度９０，平均粒径１．４μｍ）アミノシラン表面処理品 Details of each component in the table are as follows.
<Baked kaolin>
Calcined kaolin: Translink 445 (manufactured by BASF: whiteness 90, average particle size 1.4 μm) Aminosilane surface-treated product
＜防汚薬剤＞
　亜酸化銅：商品名「ＮＣ－３０１」（日進ケムコ株式会社製）
　チオシアン酸銅（I）：商品名「チオシアン酸銅（I）」（富士フイルム和光純薬工業株式会社製）
　カッパーピリチオン：商品名「カッパーオマジン」（ＬＯＮＺＡ株式会社製）
　ジンクピリチオン：商品名「ジンクオマジン」（ＬＯＮＺＡ株式会社製）
　ジネブ：商品名「ジネブ」（ＳＩＧＭＡ－ＡＬＤＲＩＣＨ製）
　ＳｅａＮｉｎｅ２１１：４，５－ジクロロ－２－ｎ－オクチル－３－イソチアゾロン（Ｒ＆Ｈ社製、有効成分３０％キシレン溶液）
　メデトミジン：商品名「Ｓｅｌｅｋｔｏｐｅ」（アイテック製）
　Ｅｃｏｎｅａ０２８：２－（ｐ－クロロフェニル）－３－シアノ－４－ブロモ－５－トリフルオロメチルピロール（ヤンセンＰＭＰ製）
　トリルフルアニド　：　商品名「Ｐｒｅｖｅｎｔｏｌ　Ａ　５－Ｓ　（Ｌａｎｘｅｓｓ社製）
　ジウロン：商品名「ジウロン」（東京化成工業社製）
　ピリジントリフェニルボラン：ＰＫ（北興化学工業社製）
　イルガロール１０５１：商品名「イルガロール１０５１」Ｎ－シクロプロピル－Ｎ'－ｔｅｒｔ－ブチル－６－（メチルチオ）－１，３，５－トリアジン－２，４－ジアミン（ＢＡＳＦ社製） <Anti-fouling agent>
Copper oxide: Product name "NC-301" (manufactured by Nissin Chemco Co., Ltd.)
Copper thiocyanate (I): Product name "Copper thiocyanate (I)" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
Copper Pirition: Product name "Copper Omagin" (manufactured by LONZA Co., Ltd.)
Zinc pyrithione: Product name "Zinc pyrithione" (manufactured by LONZA Co., Ltd.)
Zineb: Product name "Zineb" (manufactured by SIGMA-ALDRICH)
SeaNine211: 4,5-dichloro-2-n-octyl-3-isothiazolone (manufactured by R & H, 30% xylene solution of active ingredient)
Medetomidine: Product name "Selektope" (manufactured by Aitec)
Econea 028: 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)
Trill fullanid: Product name "Preventol A 5-S (manufactured by Lanxess)"
Jiuron: Product name "Jiuron" (manufactured by Tokyo Chemical Industry Co., Ltd.)
Pyridinetriphenylborane: PK (manufactured by Hokuko Chemical Industry Co., Ltd.)
Ilgarol 1051: Product name "Irgalol 1051"N-cyclopropyl-N'-tert-butyl-6- (methylthio) -1,3,5-triazine-2,4-diamine (manufactured by BASF)
＜その他の添加剤＞
　ガムロジン溶液：中国産ガムロジン（ＷＷ）の固形分５０％キシレン溶液
　ロジン亜鉛塩溶液：製造例１０で製造したものを使用
　水添ロジン溶液：商品名「ハイペールＣＨ」（荒川化学工業株式会社製）の固形分５０％キシレン溶液
　水添ロジン亜鉛塩溶液：製造例１１で製造したものを使用
　塩素化パラフィン：商品名「トヨパラックスＡ４０Ｓ」（東ソー株式会社製）
　パラフィン鉱油：商品名「ピュアセイフティー６８」（コスモ石油ルブリカンツ社製）
　トリメリット酸トリス（２－エチルヘキシル）：商品名「トリメリット酸トリス（２－エチルヘキシル）」（東京化成工業株式会社製）
　エポキシ化大豆油：商品名「サンソサイザーＥ－２０００Ｈ」（新日本理化株式会社製）
　タルク：商品名「タルクＭＳ」（日本タルク株式会社製）
　酸化亜鉛：商品名「酸化亜鉛２種」（正同化学工業株式会社製）
　ベンガラ：商品名「ベンガラキンギョク」（森下弁柄工業株式会社製）
　エチルシリケート２８：テトラエトキシシラン：商品名「エチルシリケート２８」（コルコート株式会社製）
　酸化チタン：商品名「ＦＲ－４１」（古河機械金属株式会社製）
　含水カオリン：商品名「ＡＳＰ－Ｇ９２」（東新化成株式会社製）
　ゼオライト：商品名「モレキュラーシーブ４Ａ」（ユニオン昭和社製）
　硫酸カルシウム：商品名「活性無水硫酸カルシウム」（ナカライテクス社製、試薬）
　硫酸バリウム：商品名「ＴＳ－２」（竹原化学工業社製）
　脂肪酸アマイド：商品名「ディスパロンＡ６０３－２０Ｘ」（楠本化成株式会社製）、アマイド系チクソトロピック剤
　酸化ポリエチレン：商品名「ディスパロン４２００－２０」（楠本化成株式会社製）
　フュームドシリカ：商品名「ＡＥＲＯＳＩＬ　Ｒ９７２」（エボニック社製） <Other additives>
Gum rosin solution: 50% solid content xylene solution of Chinese gum rosin (WW) Rosin zinc salt solution: Use the one produced in Production Example 10 Hydrogenated rosin solution: Under the trade name "Hyper CH" (manufactured by Arakawa Chemical Industry Co., Ltd.) Solid content 50% xylene solution Hydrogenated rosin zinc salt solution: Use the one produced in Production Example 11 Chlorinated paraffin: Trade name "Toyoparax A40S" (manufactured by Toso Co., Ltd.)
Paraffin mineral oil: Product name "Pure Safety 68" (manufactured by Cosmo Oil Lubricants)
Tristrimellitic acid (2-ethylhexyl): Product name "Tristrimellitic acid (2-ethylhexyl)" (manufactured by Tokyo Chemical Industry Co., Ltd.)
Epoxy soybean oil: Product name "Sun Sizar E-2000H" (manufactured by New Japan Chemical Co., Ltd.)
Talc: Product name "Talc MS" (manufactured by Japan Talc Co., Ltd.)
Zinc oxide: Product name "Zinc oxide 2 types" (manufactured by Shodo Chemical Industry Co., Ltd.)
Bengala: Product name "Bengala Kingyoku" (manufactured by Morishita Benji Kogyo Co., Ltd.)
Ethyl silicate 28: Tetraethoxysilane: Product name "Ethyl silicate 28" (manufactured by Corcote Co., Ltd.)
Titanium oxide: Product name "FR-41" (manufactured by Furukawa Co., Ltd.)
Hydrous Kaolin: Product name "ASP-G92" (manufactured by Toshin Kasei Co., Ltd.)
Zeolite: Product name "Molecular Sheave 4A" (manufactured by Union Showa)
Calcium sulfate: Product name "Active anhydrous calcium sulfate" (manufactured by Nacalai Tesque, reagent)
Barium sulfate: Product name "TS-2" (manufactured by Takehara Chemical Industry Co., Ltd.)
Fatty acid amide: Product name "Disparon A603-20X" (manufactured by Kusumoto Kasei Co., Ltd.), Amide-based thixotropic agent Polyethylene oxide: Product name "Disparon 4200-20" (manufactured by Kusumoto Kasei Co., Ltd.)
Fumed silica: Product name "AEROSIL R972" (manufactured by Evonik)
＜オルガノポリシロキサンＢ＞
　ＤＭＳ－Ｓ３５：商品名「ＤＭＳ－Ｓ３５」、Ｇｅｌｅｓｔ社製、両末端シラノール基を有するポリジメチルシロキサン、Ｍｗ　４９０００
　ＤＭＳ－Ｓ３２：商品名「ＤＭＳ－Ｓ３２」、Ｇｅｌｅｓｔ社製、両末端シラノール基を有するポリジメチルシロキサン、Ｍｗ　３６０００
　ＹＲ３２０４：商品名「ＹＲ３２０４」、モメンティブ社製、両末端シラノール基を有するポリメチルフェニルシロキサン（９０％溶液） <Organopolysiloxane B>
DMS-S35: Trade name "DMS-S35", manufactured by Gelest, polydimethylsiloxane having both terminal silanol groups, Mw 49000
DMS-S32: Trade name "DMS-S32", manufactured by Gelest, polydimethylsiloxane having both terminal silanol groups, Mw 36000
YR3204: Trade name "YR3204", manufactured by Momentive, polymethylphenylsiloxane (90% solution) having both terminal silanol groups.
＜ブリードオイル＞
　ポリエーテル変性シリコーンオイル：商品名「ＫＦ－６０２０」側鎖型ポリエチレンオキサイド及びポリプロピレンオキサイド変性ポリシロキサン（信越化学社製）
　ポリエーテル・長鎖アルキル・アラルキル変性シリコーンオイル：商品名「Ｘ－２２－２５１６」側鎖型ポリエチレンオキサイド、ポリプロピレンオキサイド、長鎖アルキル、アラルキル変性ポリシロキサン（信越化学社製）
　ポリオキシエチレン（３０）ラノリン：商品名「ＮＩＫＫＯＬ　ＴＷ－３０」（日光ケミカルズ社製）
　メチルフェニルシリコーンオイル：商品名「ＫＦ－５０」（信越化学社製） <Bleed oil>
Polyether-modified silicone oil: Trade name "KF-6020" Side-chain polyethylene oxide and polypropylene oxide-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)
Polyether / long-chain alkyl / aralkyl-modified silicone oil: Trade name "X-22-2516" Side-chain polyethylene oxide, polypropylene oxide, long-chain alkyl, aralkyl-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)
Polyoxyethylene (30) lanolin: Product name "NIKKOL TW-30" (manufactured by Nikko Chemicals Co., Ltd.)
Methylphenyl silicone oil: Product name "KF-50" (manufactured by Shin-Etsu Chemical Co., Ltd.)
＜縮合触媒＞
　ジブチルスズジラウレート：ジ－ｎ－ブチルスズジラウレート、商品名「ネオスタン Ｕ－１００」（日東化成製） <Condensation catalyst>
Dibutyltin dilaurate: Di-n-butyltin dilaurate, trade name "Neostan U-100" (manufactured by Nitto Kasei)
＜架橋剤＞
　テトラエトキシシランの部分加水分解縮合物：「ＴＥＳ４０　ＷＮ」（ワッカー・ケミー社製） <Crosslinking agent>
Partially hydrolyzed condensate of tetraethoxysilane: "TES40 WN" (manufactured by Wacker Chemie)
＜溶剤＞
　キシレン：（試薬、東京化成工業社製）、エチルベンゼン含有
　ジプロピレングリコール：（試薬、東京化成工業社製）
　ジエチレングリコールモノブチルエーテル（試薬、東京化成工業社製） <Solvent>
Xylene: (Reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), Dipropylene glycol containing ethylbenzene: (Reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
Diethylene glycol monobutyl ether (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
３．評価
　実施例・比較例の塗料組成物について、以下に示す試験を行った。その結果を表１～表５に示す。表１～表５に示すように、樹脂成分Ｒ及び焼成カオリン含む組成物を用いて形成した塗膜は、長期間太陽光に暴露された後においても長期間にわたり塗膜溶解が持続し、良好な防汚性能を発揮できることが分かった。 3. 3. Evaluation The following tests were conducted on the coating compositions of Examples and Comparative Examples. The results are shown in Tables 1 to 5. As shown in Tables 1 to 5, the coating film formed by using the composition containing the resin component R and the calcined kaolin is good because the coating film dissolution continues for a long period of time even after being exposed to sunlight for a long period of time. It was found that it can exhibit excellent antifouling performance.
＜耐候性試験＞
　実施例１～２３及び比較例１～６については、塗料組成物を硬質塩ビ版（１００×２００×２ｍｍ）の両面に乾燥塗膜として厚みが約２００μｍとなるように塗布した。得られた塗布物を室温（２５℃）で３日乾燥させることにより、厚みが約２００μｍの乾燥塗膜を有する試験板を作成した。 <Weather resistance test>
In Examples 1 to 23 and Comparative Examples 1 to 6, the coating composition was applied to both sides of a hard vinyl chloride plate (100 × 200 × 2 mm) as a dry coating film so as to have a thickness of about 200 μm. The obtained coating film was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 200 μm.
　実施例２４～２６及び比較例７については、エポキシ系プライマーＨＥＭＰＡＤＵＲ　ＱＵＡＴＴＲＯ　ＸＯ　１７８７０（ＨＥＭＰＥＬ社製）を硬質塩ビ板（１１０×６０×２ｍｍ）上に乾燥膜厚で約１００μｍ塗布した後、さらにシリコン系タイコートＨＥＭＰＡＳＩＬ　ＮＥＸＵＳ　Ｘ－ＴＥＮＤ　２７５００（ＨＥＭＰＥＬ社製）を乾燥膜厚で約１００μｍ塗布した。この上に、実施例・比較例で得られた防汚塗料組成物のａ液とｂ液を混合したものを乾燥膜厚で約２００μｍ塗布し、室温で３日間乾燥させて試験板を作製した。 In Examples 24 to 26 and Comparative Example 7, an epoxy-based primer HEMPADUR QUATTRO XO 17870 (manufactured by HEMPEL) was applied on a hard vinyl chloride plate (110 × 60 × 2 mm) with a dry film thickness of about 100 μm, and then further silicon-based. Tiecoat HEMPASIL NEXUS X-TEND 27500 (manufactured by HEMPEL) was applied in a dry film thickness of about 100 μm. A mixture of solutions a and b of the antifouling coating composition obtained in Examples and Comparative Examples was applied thereto with a dry film thickness of about 200 μm, and dried at room temperature for 3 days to prepare a test plate. ..
　この試験板を屋外で南向きに地上から４５°の角度で太陽放射を暴露し、３ヶ月後、６ヶ月後の塗膜状態を評価した。評価は以下の方法で行った。
〇：まったく異常がない。
×：塗膜にクラックが見られる。

＜耐候性試験後の浸漬試験＞
　上記の耐候性試験を６ヶ月行った後の試験板を、三重県尾鷲市の海面下１．５ｍに浸漬して付着物による試験板の汚損を６ヶ月後、１２ヶ月後、１８ヶ月後、２４ヶ月後に観察した。
評価は塗膜表面の状態を目視観察することにより行い、以下の基準で判断した。
◎：貝類や藻類などの汚損生物付着がなく、かつ、スライムも殆どなし。
〇：貝類や藻類などの汚損生物の付着がなく、かつ、スライムが薄く（塗膜面が見える程度）付着しているものの刷毛で軽く拭いて取れるレベル。
△：貝類や藻類などの汚損生物の付着はないが、塗膜面が見えない程度スライムが厚く付着しており、刷毛で強く拭いても取れないレベル。
×：貝類や藻類などの汚損生物が付着しているレベル。 This test plate was exposed to solar radiation outdoors at an angle of 45 ° from the ground facing south, and the state of the coating film after 3 months and 6 months was evaluated. The evaluation was performed by the following method.
〇: There is no abnormality at all.
X: Cracks are seen in the coating film.

<Immersion test after weather resistance test>
After performing the above weather resistance test for 6 months, the test plate was immersed 1.5 m below the sea level in Owase City, Mie Prefecture to stain the test plate with deposits after 6 months, 12 months, and 18 months. Observed after 24 months.
The evaluation was performed by visually observing the state of the coating film surface, and judged according to the following criteria.
◎: There is no adhesion of polluted organisms such as shellfish and algae, and there is almost no slime.
〇: A level at which there is no attachment of polluted organisms such as shellfish and algae, and slime is thinly attached (to the extent that the coating film surface can be seen), but it can be lightly wiped off with a brush.
Δ: There is no adhesion of polluted organisms such as shellfish and algae, but the slime is so thick that the coating film surface cannot be seen, and it cannot be removed even if it is wiped strongly with a brush.
×: Level at which polluted organisms such as shellfish and algae are attached.

Claims (3)

  1. 　樹脂成分Ｒおよび焼成カオリンを含有する防汚塗料組成物であって、
    　前記樹脂成分Ｒは、共重合体Ａであるか、又は架橋反応性官能基を有するオルガノポリシロキサンＢであり、
    　前記共重合体Ａは、単量体（ａ）と、前記単量体（ａ）以外のエチレン性不飽和単量体（ｂ）との共重合体であり、
    　前記単量体（ａ）は、一般式（１）で表される、防汚塗料組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１は水素原子又はメチル基、Ｒ２～Ｒ４はそれぞれ同一又は異なって炭素数３～８の分岐アルキル基又はフェニル基を示す）     An antifouling coating composition containing a resin component R and calcined kaolin.
    The resin component R is a copolymer A or an organopolysiloxane B having a cross-linking reactive functional group.
    The copolymer A is a copolymer of the monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a).
    The monomer (a) is an antifouling coating composition represented by the general formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 to R 4 represent the same or different branched alkyl group or phenyl group having 3 to 8 carbon atoms, respectively).
  2. 　請求項１に記載の防汚塗料組成物であって、
    　前記樹脂成分Ｒは、前記共重合体Ａである、防汚塗料組成物。     The antifouling coating composition according to claim 1.
    The resin component R is an antifouling coating composition which is the copolymer A.
  3. 　請求項１に記載の防汚塗料組成物であって、
    　前記樹脂成分Ｒは、前記オルガノポリシロキサンＢである、防汚塗料組成物。     The antifouling coating composition according to claim 1.
    The resin component R is an antifouling coating composition which is the organopolysiloxane B.
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